[HgCl(2,5-diformylphenyl)] | 198643-97-9

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: [HgCl(2,5-diformylphenyl)]
• CAS: 198643-97-9
• 化学式: C₈H₅ClHgO₂
• 分子量: 369.17
• InChiKey: NTGFZTHITHXZHG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.85
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [HgCl(2,5-diformylphenyl)] 在 H₂SO₄ 、 (CH₃)4NCl 作用下， 以 甲醇 、 丙酮 为溶剂， 生成 [Pd(C6H3(CH(OMe)2)2-2,5)Cl(2,2'-bipyridine)]
  参考文献：
  名称：

  Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes

  摘要：

  The arylmercurial [Hg{C6H3(CHO)(2)-2,5}Cl] (1) reacts with CH(OMe)(3) or HS(CH2)(2)SH to give [Hg{C6H3{CH(OMe)(2)}(2)-2,5}Cl] (2) or [Hg(Ar-a)Cl] [Ar-a = C6H3{CH(SCH2CH2S)}(2)-2,5 (3a)], respectively. The mercurial 2 or 3a reacts with (NMe4)(2)[Pd2Cl6] and 2,2'-bipyridine (bpy) or with trans- [PdCl2(PPh3)(2)] to give the aryl-palladium complex [Pd{C6H3{CH(OMe)(2)}(2)-2,5}Cl(bpy)] (4) or [Pd(kappa(2)-C,S-Ar-a)Cl(PPh3)] (5a*), respectively. The reaction of 1 with NaI3 renders IC6H3(CHO)(2)-2,5 (6), which reacts with HS(CH2)(2)SH to give IAra (7a). Similarly, IC6H(OMe)(3)-2,3,4-(CHO)-6 (8) reacts with HS(CH2)(2)SH or ToSH (To = C6H4Me-4) to give the corresponding dithioacetals IAX(b) [Ar-b = C6H(OMe)(3)-2,3,4-{CH(SCH2CH2S)}-6 (7b)] or IC6H(OMe)(3)-2,3,4-CH(STo)(2)-6 (9). The iodoarene 7a or 7b adds oxidatively to "Pd(dba)(2)" (dba = dibenzylideneacetone) to give [Pd(kappa(2)-C, S-Ar)(mu-I)](2) [Ar = Ar-a (10a), Ar-b (10b)], which, in turn, reacts (i) with 1 equiv of PPh3 to give [Pd(kappa(2)-C,S-Ar)I(PPh3)] [Ar = Ar-a (5a), Ar-b (5b)], (ii) with Tl(TfO) (TfO = CF3SO3) and PPh3 (1:2:4 molar ratio) to give [Pd(kappa(2)-C, S-Ar-b)(PPh3)(2)]TfO (11b), or (iii) with 1 equiv of Tl(TfO) and bpy (1:2:2 molar ratio) to give [Pd(kappa(2)-C, S-Arb)(bpy)]TfO (11b*). Complexes 10 react with 1 equiv of isonitriles to give, after a short period of reaction, the complexes [Pd(kappa(2)-C,S-Ar)I(CNR)] [Ar = Ar-a, R = Xy = 2,6-dimethylphenyl (12a), Bu-t (12a'); Ar = Ar-b, R = Bu-t (12b')]. The iminoacyl complexes [Pd(kappa(2)-C,S-Im)(mu-I](2) [Im = Im(a) (13a), Im(b) (13b)] can be obtained by stirring a solution of 12a for 5 days to give 13a or by reacting 10b with XyNC in 1:1 molar ratio during 22 h to give 13b. Complexes 10 react with 2 equiv of isonitriles to give the iminoacyl complexes [Pd(kappa(2)-C,S-Im)l(CNR)] [Im = C(=NR)C6H3-{CH(SCH2CH2S)}(2)-2,5, R = Xy, Im = Im(a) (14a), R = Bu-t, Im = Im(a')(14a'); Im = C(=NR)C6H(OMe)(3)-2,3,4-(SCH2CH2S)-6, R = Xy, Im = Im(b) (14b), R = Bu-t, Im = Im(b)' (14b')]. Complexes 14a,b react with 10a,b in 2:1 molar ratio to give 13a,b. Complexes 10a,b react with XyNC and Tl(TfO) (1:4:1) to give the dimeric cations [Pd{(kappa(2)-C,S-Im)(CNXy)}(2)(mu-I)]TfO [R = Xy, Im = im(a) (15a), Im(b) (15b)].The compound [Pd{kappa(2)-C,S-Ar-c}(mu-I)](2) (16) reacts (i) with PPh3 and Tl(TfO) in 1:4:2 molar ratio to give [Pd-II(kappa(2)-C,S-Ar-c)(PPh3)(2)]TfO <----> [Pd-0{eta(2)-kappa(3)-C,S,S-S(To)=CHC6H(STo)-2-(OMe)(3)-3,4,5}(PPh3)(2)]TfO (17), (ii) with isonitriles in 1:2 or 1:4 molar ratio yielding complexes [Pd(kappa(2)-C,S-Ar-c)I(CNR)] [R = Xy (18), R = Bu-t (18')] or trans-[Pd(kappa(1)-C-Ar-c)I(CNR)(2)] [R = Xy (19), R = Bu-t (19')], respectively, and (iii) with PPh3 in 1:2 molar ratio yielding [Pd(kappa(2)-C,S-Ar-c)I(PPh3)] (20). The iodoarene 9 reacts with Pd(dba)(2) (i) and PPh3 (1:1:1 molar ratio) to give [Pd{kappa(2)-C,S-Ar-c)I(PPh3)] [Ar-c = CH(STo)C6H(STo)-2-(OMe)(3)-3,4,5(20)] and (ii) PPh3 and Tl(TfO) (1: 1:2:1 molar ratio) to give 17. The crystal and molecular structures of 4, 5a*, 14a, and 14b have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om0342964
• 作为产物：
  描述：

  对苯二甲醛 、 sodium chloride 、 mercury(II) oxide 以 水 为溶剂， 以39%的产率得到[HgCl(2,5-diformylphenyl)]
  参考文献：
  名称：

  通过金属化，过渡金属化，氧化和缩合反应合成对苯甲醛的汞（II）和钯（II）有机金属衍生物。反式-[PdCl {C 6 H 3（CO 2 H）2 -2,5}（PPh 3）2 ]·Me 2 CO·2MeOH，反式-[PdCl {C 6 H 3（CHO ）的X射线晶体结构）-2-（CO 2 H）-5}（PPh 3）2 ]·2CH 2 Cl 2和[Pd {C 6 H 3（CHNC 6 H 4 NH 2）-4）-2-（CHO）-5}（N，N，N '，N'-四甲基乙二胺）] CF 3 SO 3。通过[Pd] -Cl···HO 2 C-芳基和[Pd] -Cl···HOMe HO（O）C-芳基氢键的分子组装†

  摘要：

  有机汞[HgCl {C 6 H 3（CHO）2 -2,5}]（1）和[Hg {C 6 H 3（CHO）2 -2,5} 2 ]（2）已通过汞化制备。对苯二甲醛。钯配合物[PdCl {C 6 H 3（CHO）2 -2,5}（NN）]（NN = N，N，N '，N'-四甲基乙二胺（tmeda）（3）或2,2'-联吡啶（ bpy）（3 '））或反式-[PdCl {C 6 H 3（CHO）通过使（Me 4 N）2 [Pd 2 Cl 6 ]或反式-[PdCl 2（PPh 3）2 ]分别获得2 -2,5}（PPh 3）2 ]·H 2 O（4），带有1或2。高锰酸钾与配合物3和3 '或汞1的反应导致5-甲酰基取代基的选择性氧化，从而提供[PdCl {C 6 H 3（CHO）-2-（CO 21H）-5}（NN）]（NN = TMEDA（5），联吡啶（5 “））或分别的混合物的主要成分是完全氧化的[{的HgClÇ

  DOI：

  10.1021/om970583u

文献信息

• Synthesis and Reactivity of <i>Ortho</i>-Mercuriated and <i>Ortho</i>-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes
  作者：José Vicente、José-Antonio Abad、Francisco S. Hernández-Mata、Barbara Rink、Peter G. Jones、M. Carmen Ramírez de Arellano

  DOI：10.1021/om0342964

  日期：2004.3.1

  The arylmercurial [HgC6H3(CHO)(2)-2,5}Cl] (1) reacts with CH(OMe)(3) or HS(CH2)(2)SH to give [HgC6H3CH(OMe)(2)}(2)-2,5}Cl] (2) or [Hg(Ar-a)Cl] [Ar-a = C6H3CH(SCH2CH2S)}(2)-2,5 (3a)], respectively. The mercurial 2 or 3a reacts with (NMe4)(2)[Pd2Cl6] and 2,2'-bipyridine (bpy) or with trans- [PdCl2(PPh3)(2)] to give the aryl-palladium complex [PdC6H3CH(OMe)(2)}(2)-2,5}Cl(bpy)] (4) or [Pd(kappa(2)-C,S-Ar-a)Cl(PPh3)] (5a*), respectively. The reaction of 1 with NaI3 renders IC6H3(CHO)(2)-2,5 (6), which reacts with HS(CH2)(2)SH to give IAra (7a). Similarly, IC6H(OMe)(3)-2,3,4-(CHO)-6 (8) reacts with HS(CH2)(2)SH or ToSH (To = C6H4Me-4) to give the corresponding dithioacetals IAX(b) [Ar-b = C6H(OMe)(3)-2,3,4-CH(SCH2CH2S)}-6 (7b)] or IC6H(OMe)(3)-2,3,4-CH(STo)(2)-6 (9). The iodoarene 7a or 7b adds oxidatively to "Pd(dba)(2)" (dba = dibenzylideneacetone) to give [Pd(kappa(2)-C, S-Ar)(mu-I)](2) [Ar = Ar-a (10a), Ar-b (10b)], which, in turn, reacts (i) with 1 equiv of PPh3 to give [Pd(kappa(2)-C,S-Ar)I(PPh3)] [Ar = Ar-a (5a), Ar-b (5b)], (ii) with Tl(TfO) (TfO = CF3SO3) and PPh3 (1:2:4 molar ratio) to give [Pd(kappa(2)-C, S-Ar-b)(PPh3)(2)]TfO (11b), or (iii) with 1 equiv of Tl(TfO) and bpy (1:2:2 molar ratio) to give [Pd(kappa(2)-C, S-Arb)(bpy)]TfO (11b*). Complexes 10 react with 1 equiv of isonitriles to give, after a short period of reaction, the complexes [Pd(kappa(2)-C,S-Ar)I(CNR)] [Ar = Ar-a, R = Xy = 2,6-dimethylphenyl (12a), Bu-t (12a'); Ar = Ar-b, R = Bu-t (12b')]. The iminoacyl complexes [Pd(kappa(2)-C,S-Im)(mu-I](2) [Im = Im(a) (13a), Im(b) (13b)] can be obtained by stirring a solution of 12a for 5 days to give 13a or by reacting 10b with XyNC in 1:1 molar ratio during 22 h to give 13b. Complexes 10 react with 2 equiv of isonitriles to give the iminoacyl complexes [Pd(kappa(2)-C,S-Im)l(CNR)] [Im = C(=NR)C6H3-CH(SCH2CH2S)}(2)-2,5, R = Xy, Im = Im(a) (14a), R = Bu-t, Im = Im(a')(14a'); Im = C(=NR)C6H(OMe)(3)-2,3,4-(SCH2CH2S)-6, R = Xy, Im = Im(b) (14b), R = Bu-t, Im = Im(b)' (14b')]. Complexes 14a,b react with 10a,b in 2:1 molar ratio to give 13a,b. Complexes 10a,b react with XyNC and Tl(TfO) (1:4:1) to give the dimeric cations [Pd(kappa(2)-C,S-Im)(CNXy)}(2)(mu-I)]TfO [R = Xy, Im = im(a) (15a), Im(b) (15b)].The compound [Pdkappa(2)-C,S-Ar-c}(mu-I)](2) (16) reacts (i) with PPh3 and Tl(TfO) in 1:4:2 molar ratio to give [Pd-II(kappa(2)-C,S-Ar-c)(PPh3)(2)]TfO <----> [Pd-0eta(2)-kappa(3)-C,S,S-S(To)=CHC6H(STo)-2-(OMe)(3)-3,4,5}(PPh3)(2)]TfO (17), (ii) with isonitriles in 1:2 or 1:4 molar ratio yielding complexes [Pd(kappa(2)-C,S-Ar-c)I(CNR)] [R = Xy (18), R = Bu-t (18')] or trans-[Pd(kappa(1)-C-Ar-c)I(CNR)(2)] [R = Xy (19), R = Bu-t (19')], respectively, and (iii) with PPh3 in 1:2 molar ratio yielding [Pd(kappa(2)-C,S-Ar-c)I(PPh3)] (20). The iodoarene 9 reacts with Pd(dba)(2) (i) and PPh3 (1:1:1 molar ratio) to give [Pdkappa(2)-C,S-Ar-c)I(PPh3)] [Ar-c = CH(STo)C6H(STo)-2-(OMe)(3)-3,4,5(20)] and (ii) PPh3 and Tl(TfO) (1: 1:2:1 molar ratio) to give 17. The crystal and molecular structures of 4, 5a*, 14a, and 14b have been determined by X-ray diffraction studies.
• Synthesis of Mercury(II) and Palladium(II) Organometallic Derivatives of Terephthaldehyde by Metalation, Transmetalation, Oxidation, and Condensation Reactions. X-ray Crystal Structures of <i>trans</i>-[PdCl{C₆H₃(CO₂H)₂-2,5}(PPh₃)₂]·Me₂CO·2MeOH, <i>trans</i>-[PdCl{C₆H₃(CHO)-2-(CO₂H)-5}(PPh₃)₂]·2CH₂Cl₂, and [Pd{C₆H₃(CHNC₆H₄NH₂-4)-2-(CHO)-5}(<i>N</i>,<i>N</i>,<i>N</i>‘,<i>N</i>‘-Tetramethylethylenediamine)]CF₃SO₃. Molecular Assemblies through [Pd]−Cl···HO₂C−Aryl and [Pd]−Cl···HOMe  HO(O)C−Aryl Hydrogen Bonds
  作者：José Vicente、José-Antonio Abad、Barbara Rink、Francisco-Santos Hernández、M. Carmen Ramírez de Arellano

  DOI：10.1021/om970583u

  日期：1997.11.1

  5}] (1) and [HgC6H3(CHO)2-2,5}2] (2) have been prepared by mercuriation of terephthaldehyde. Palladium complexes [PdClC6H3(CHO)2-2,5}(N-N)] (N-N = N,N,N‘,N‘-tetramethylethylenediamine (tmeda) (3) or 2,2‘-bipyridine (bpy) (3‘)) or trans-[PdClC6H3(CHO)2-2,5}(PPh3)2]·H2O (4) have been obtained by reacting (Me4N)2[Pd2Cl6] or trans-[PdCl2(PPh3)2], respectively, with 1 or 2. The reaction of potassium permanganate

  有机汞[HgCl C 6 H 3（CHO）2 -2,5}]（1）和[Hg C 6 H 3（CHO）2 -2,5} 2 ]（2）已通过汞化制备。对苯二甲醛。钯配合物[PdCl C 6 H 3（CHO）2 -2,5}（NN）]（NN = N，N，N '，N'-四甲基乙二胺（tmeda）（3）或2,2'-联吡啶（ bpy）（3 '））或反式-[PdCl C 6 H 3（CHO）通过使（Me 4 N）2 [Pd 2 Cl 6 ]或反式-[PdCl 2（PPh 3）2 ]分别获得2 -2,5}（PPh 3）2 ]·H 2 O（4），带有1或2。高锰酸钾与配合物3和3 '或汞1的反应导致5-甲酰基取代基的选择性氧化，从而提供[PdCl C 6 H 3（CHO）-2-（CO 21H）-5}（NN）]（NN = TMEDA（5），联吡啶（5 “））或分别的混合物的主要成分是完全氧化的[的HgClÇ